EP0198682B1 - Alkoholherstellung durch Hydrogenierung von Carbonsäuren - Google Patents

Alkoholherstellung durch Hydrogenierung von Carbonsäuren Download PDF

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Publication number
EP0198682B1
EP0198682B1 EP86302692A EP86302692A EP0198682B1 EP 0198682 B1 EP0198682 B1 EP 0198682B1 EP 86302692 A EP86302692 A EP 86302692A EP 86302692 A EP86302692 A EP 86302692A EP 0198682 B1 EP0198682 B1 EP 0198682B1
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Prior art keywords
catalyst
process according
support
noble metal
group viii
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EP86302692A
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English (en)
French (fr)
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EP0198682A2 (de
EP0198682A3 (en
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Melanie Kitson
Peter Sefton Williams
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BP Chemicals Ltd
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BP Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/525—Perovskite

Definitions

  • the present invention relates to the catalysed hydrogenation of carboxylic acids to produce the corresponding alcohol and/or carboxylic acid ester.
  • USP-A-4524225 describes the hydrogenation of C6-C 24 fatty acids by contacting the fatty acid with hydrogen at 100 to 300°C and 100 to 3000 psig in the presence of a zerovalent metal selected from Cu, Cr, Ru, Pt, Pd, Re and mixtures thereof dispersed on a support which may be alpha, theta or titanated alumina, titania, or AlPO4 or a mixture thereof.
  • USP-A-4104478 describes the production of C4 to C 24 fatty alcohols by catalytically hydrogenating the corresponding fatty acid at 170 to 250°C and 20 to 140 atmospheres over a catalyst system consisting of (a) 1 part wt. of activated Re, and (b) 0.25 to 1.5 parts of an extrinsic metal catalyst selected from Ru, Rh, Pt and Pd.
  • GB-A-1534232 describes the preparation of alcohols by catalytic hydrogenation of carboxylic acids at elevated temperature and pressure in the presence of water and/or solvents using a Pd/Re catalyst on a support, the catalyst having a Pd : Re wt ratio of 0.01 to 5 : 1.
  • GB-A-1551741 describes the one-step preparation of 1,4-butanediol from maleic acid by hydrogenation in the presence of a catalyst containing (A) elements of Group VII, preferably Mn or Re, or their compounds, and (B) elements of Group VIII, preferably Ru, Rh, Pd, Os, Ir or Pt, more preferably Pd or Pt or their compounds or mixtures thereof.
  • A elements of Group VII, preferably Mn or Re, or their compounds
  • B elements of Group VIII, preferably Ru, Rh, Pd, Os, Ir or Pt, more preferably Pd or Pt or their compounds or mixtures thereof.
  • DE-A-3221077 describes the continuous production of ethanol by the hydrogenation of acetic acid at elevated pressure and temperature using a catalyst based on Co.
  • EP-A-147219 published after the priority date claimed for the subject application on an application claiming an earlier priority date, describes the hydrogenation of maleic acid using a Pd/Re/C catalyst.
  • Russian Patent number 420326 describes a process for preparing catalysts for hydrogenation of organic compounds, eg aliphatic acids, by permeating spheroid synthetic aluminosilicate with an aqueous-spirit solution of a complex salt of palladium, with subsequent drying, heating to 110°C and reducing in a flow of hydrogen, characterised in that with the aim of raising the activity, mechanical strength, stability and regeneration capacity of the catalyst, the catalyst is permeated before reduction with aqueous salts of metals of Group VI eg sulphates, ammonium sulphates or nitrates of chromium, molybdenum or tungsten or a vanadium salt in a ratio 1: 1-1: 10.
  • the only example given is of the use of chromium nitrate.
  • the hydrogenation process is recommended for the production of toilet and household soaps and for the production of stearin.
  • the present invention provides a process for the production of an alcohol and/or a carboxylic acid ester from a C2 to C 12 carboxylic acid by contacting the carboxylic acid at elevated temperature and pressure with hydrogen in the presence of a heterogeneous catalyst characterised in that the catalyst comprises a first component which is either molybdenum or tungsten and a second component which is a noble metal of Group VIII of the Periodic Table of the Elements.
  • the process of the invention generally also produces the corresponding ester as a by-product, for example the hydrogenation of acetic acid generally also produces ethyl acetate and the hydrogenation of propionic acid generally also produces propyl propionate.
  • the proportion of the ester in the product will depend on the nature of the catalyst, for example tungsten-containing catalysts will generally produce higher proportions of the ester, and on the reaction conditions, for example the formation of esters is favoured by operating at low conversions, for example less than 50% per pass.
  • the proportion of ester in the product may be further increased, if desired, by feeding additional carboxylic acid and/or by introducing an acidic function into the catalyst to promote ⁇ in situ ⁇ esterification. It is possible, therefore, to produce a product substantially comprising the carboxylic acid ester, particularly by operating in the liquid phase at low conversions, for example less than 50%.
  • C2 to C 12 carboxylic acid there may suitably be used either a saturated or an unsaturated carboxylic acid, preferably a saturated carboxylic acid.
  • Both mono- and poly-basic carboxylic acids for example dibasic carboxylic acids, may be employed.
  • Suitable monobasic acids include acids having the formula R-COOH wherein R is a substituted or unsubstituted aliphatic, aromatic or araliphatic group, which acids are hydrogenated to alcohols of the formula RCH2OH.
  • suitable acids include acetic, propionic, butyric, heptanoic, succinic, glutaric, maleic and fumaric acids.
  • Hydrogen is commercially available on a large scale and may be used with or without further purification.
  • the catalyst comprises a first component which is either molybdenum or tungsten and a second component which is a noble metal of Group VIII.
  • the noble metals of Group VIII are the metals osmium, palladium, platinum, rhodium, ruthenium and iridium. Of the aforesaid metals palladium, rhodium and ruthenium are preferred.
  • the catalyst preferably further includes, as a third component, a support. Suitable supports include high surface area graphitised carbons, graphites, silicas, aluminas and silica/aluminas, of which high surface area graphitised carbons and silicas are preferred.
  • Particularly suitable supports are the high surface area graphitised carbons described in GB-A-2136704.
  • the carbon is preferably in particulate form e.g. as pellets.
  • the size of the carbon particles will depend on the pressure drop acceptable in any given reactor (which gives a minimum pellet size) and reactant diffusion constraint within the pellet (which gives a maximum pellet size).
  • the preferred minimum pellet size is 0.5 mm and the preferred maximum is 10 mm, e.g. not more than 5 mm.
  • the carbons are preferably porous carbons. With the preferred particle sizes the carbon will need to be porous to meet the preferred surface area charateristics.
  • Carbons may be characterised by their BET, basal plane, and edge surface areas.
  • the BET surface area is the surface area determined by nitrogen adsorption using the method of Brunauer Emmett and Teller J. Am. Chem. Soc. 60,309 (1938).
  • the basal plane surface area is the surface area determined from the heat of adsorption on the carbon of n-dotriacontane from n-heptane by the method described in Proc. Roy. Soc. A314 pages 473-498, with particular reference to page 489.
  • the edge surface area is the surface area determined from the heat of adsorption on the carbon of n-butanol from n-heptane as disclosed in the Proc. Roy. Soc. article mentioned above with particular reference to page 495.
  • the preferred carbons for use in the present invention have a BET surface area of at least 100 m2/g, more preferably at least 200 m2/g, most preferable at least 300 m2/g.
  • the BET surface area is preferably not greater than 1000 m2/g, more preferably not greater than 750 m2/g.
  • the ratio of BET to basal plane surface area is preferably not greater than 4: 1, more preferably not greater than 2.5: 1. It is particularly preferred to use carbons with ratios of BET to basal plane surface area of not greater than 1.5: 1.
  • carbons with ratios of basal plane surface area to edge surface area of at least 10: 1, preferably at least 100: 1. It is not believed that there is an upper limit on the ratio, although in practice it will not usually exceed 200: 1.
  • the preferred carbon support may be prepared by heat treating a carbon-containing starting material.
  • the starting material may be an oleophilic graphite e.g. prepared as disclosed in GB 1,168,785 or may be a carbon black.
  • oleophilic graphites contain carbon in the form of very fine particles in flake form and are therefore not very suitable materials for use as catalyst supports. We prefer to avoid their use. Similar considerations apply to carbon blacks which also have a very fine particle size.
  • the preferred materials are activated carbons derived from vegetable materials e.g. coconut charcoal, or from peat or coal or from carbonizable polymers.
  • the materials subjected to the heat treatment preferably have particle sizes not less than those indicated above as being preferred for the carbon support.
  • the preferred starting materials have the following characteristics: BET surface area of at least 100, more preferably at least 500 m2/g.
  • the preferred heat treatment procedure for preparing carbon supports having the defined characteristics comprise successively (1) heating the carbon in an inert atmosphere at a temperature of from 900°C to 3300°C, (2) oxidizing the carbon at a temperature between 300°C and 1200°C, (3) heating in an inert atmosphere at a temperature of between 900°C and 3000°C.
  • the oxidation step is preferably carried out at temperatures between 300° and 600°C when oxygen (e.g. as air) is used as the oxidising agent.
  • oxygen e.g. as air
  • the duration of the heating in inert gas is not critical. The time needed to heat the carbon to the required maximum temperature is sufficient to produce the required changes in the carbon.
  • the oxidation step must clearly not be carried out under conditions such that the carbon combusts completely. It is preferably carried out using a gaseous oxidizing agent fed at a controlled rate to avoid over oxidation.
  • gaseous oxidising agents are steam, carbon dioxide, and gases containing molecular oxygen e.g. air.
  • the oxidation is preferably carried out to give a carbon weight loss of at least 10% wt based on weight of carbon subjected to the oxidation step, more preferably at least 15% wt.
  • the weight loss is preferably not greater than 40% wt of the carbon subjected to the oxidation step, more preferably not greater than 25% wt of the carbon.
  • the rate of supply of oxidizing agent is preferably such that the desired weight loss takes place over at least 2 hours, more preferably at least 4 hours.
  • inert atmosphere may be supplied by nitrogen or an inert gas.
  • Preferred silica supports are those having a high surface area, typically greater than 50 m2/g.
  • the catalyst comprises from 0.1 to 20% by weight, preferably from 1 to 10% by weight of the first component, from 0.1 to 20% by weight, preferably from 1 to 10% by weight of the second component, the remainder of the catalyst comprising a support.
  • the catalyst may be further modified by incorporation of a metal or metals of Group IA, Group IIA or Group IVA, preferably a metal of Group IA of the Periodic Table of the Elements.
  • a suitable metal is potassium.
  • the amount of the modifying metal(s) may suitably be in the range from 1 to 20% by weight, based on the total weight of the catalyst.
  • the addition of the aforesaid modifying metals to the catalyst can have the advantageous effect that carbon-carbon bond hydrogenolysis can be suppressed to a greater or lesser extent during the carboxylic acid hydrogenation, thereby improving the selectivity of the process to desirable products.
  • the catalyst may suitably be prepared by any of the methods conventionally employed for the production of catalysts, for example by impregnation, including both co-impregnation and sequential impregnation, precipitation, including both co-precipitation and sequential precipitation, and by vapour deposition of the metals on the support.
  • impregnation including both co-impregnation and sequential impregnation
  • precipitation including both co-precipitation and sequential precipitation
  • vapour deposition of the metals on the support for example by impregnation, including both co-impregnation and sequential impregnation, precipitation, including both co-precipitation and sequential precipitation, and by vapour deposition of the metals on the support.
  • Techniques for effecting the aforesaid methods are well-known in the art and require no further elaboration.
  • a suitable method of producing a catalyst for use in the process of the present invention comprises the steps of:
  • the solvent used in steps (A) and (C) of the process may be any suitable solvent, for example water.
  • the Group VIII noble metal on the support may suitably be heated in the presence of either an inert gas, for example nitrogen, a reducing gas, for example hydrogen, or an oxygen-containing gas, for example oxygen or air. Heating in the presence of an inert gas may suitably be accomplished at an elevated temperature in the range from 150 to 350°C. Heating in the presence of a reducing gas may suitably be accomplished at an elevated temperature in the range from 100 to 350°C. Heating in the presence of an oxygen-containing gas may suitably be accomplished at an elevated temperature in the range from 100 to 300°C, provided that when a high surface area graphitised carbon is used as support the upper temperature limit is 200°C.
  • an inert gas for example nitrogen
  • a reducing gas for example hydrogen
  • an oxygen-containing gas for example oxygen or air.
  • step (A) a further step is interposed between step (A) and step (B) wherein the Group VIII noble metal impregnated support is dried, suitably by heating at a temperature in the range from 50 to 150°C. It will be appreciated by those skilled in the art that this step may be incorporated into step (B), if desired.
  • Suitable molybdenum or tungsten compounds which are decomposable/reducible to the metal and/or oxide include salts of the metals and salts wherein the metals are present in the anionic moiety, for example, ammonium molybdate or ammonium tungstate.
  • Suitable noble metal compounds which are decomposable/reducible to the noble metal include, for example, noble metal salts such as the carboxylates, halides and nitrates and ammonium salts containing the noble metal in the anion moiety, for example ammonium tetrachloropalladate.
  • the metal of Group IA, Group IIA or Group IVA of the Periodic Table of the elements may be added to the catalyst composition at any point during its preparation.
  • the supported noble metal/molybdenum or tungsten catalyst may be impregnated with a solution of a soluble compound of the metal.
  • a soluble compound of the metal may be added to the co-impregnation solution or either of the sequential impregnation solutions.
  • a preferred catalyst comprises palladium and molybdenum or tungsten supported on a high surface area graphitised carbon of the type described in the aforesaid GB-A-2136704.
  • the catalyst Before use in the process of the invention the catalyst is preferably activated by contact at elevated temperature with either hydrogen or a hydrogen/inert gas, for example nitrogen, mixture, suitably for a period of from 1 to 20 hours.
  • the elevated temperature may suitably be in the range from 200 to 350°C.
  • the catalyst may be activated by heating to the reaction temperature in the presence of reactants.
  • the Group VIII noble metal component is in the form of the elemental metal and the molybdenum or tungsten component is in the form of the elemental metal and/or an oxide thereof.
  • the process of the invention may suitably be operated at an elevated temperature in the range from 100 to 300°C, preferably from 150 to 250°C.
  • the pressure may suitably be less than 50 bar.
  • the process may be operated in the liquid phase or the vapour phase.
  • the process may be operated batchwise or continuously, preferably continuously.
  • the catalyst may be employed in the form of a fixed bed, a moving bed or a fluidised bed.
  • the Gas Hourly Space Velocity for continuous operation may suitably be in the range from 50 to 50,000 h -1 , preferably from 2,000 to 30,000 h -1 .
  • the present invention provides a catalyst for use in the process as hereinbefore described which comprises a first component which is either molybdenum or tungsten and a second component which is a noble metal of Group VIII of the Periodic Table of the Elements.
  • HSAG carbon denotes high surface area graphitised carbon, prepared and characterised as follows:
  • the carbon used as support was prepared from a commercially available activated carbon sold by Degussa under the designation BK IV.
  • the activated carbon was heat treated as follows. The carbon was heated from room temperature in a stream of argon to 1700°C over a period of about one hour. When the temperature reached 1700°C the carbon was allowed to cool in the stream of argon to 25°C. The carbon was then heated in air in a muffle furnace at approximately 520°C for a time known from experience to give a weight loss of 20% wt. The carbon was then heated in argon to between 1800°C and 1850°C in argon. The carbon was allowed to cool to room temperature in an argon atmosphere. The resulting graphite-containing carbon was then ground to 16-30 mesh BSS.
  • the resulting carbon had the following properties:
  • nominal loading is defined as weight of metal (not salt) added to the support expressed as a percentage of the weight of support.
  • Temperature was measured by means of a thermocouple inserted into the catalyst bed.
  • the product mixtures typically contained the appropriate alcohol and ester (the latter formed by esterification of alcohol with unreacted acid), together with traces of the appropriate dialkyl ether, and aldehyde, and by product methane and ethane.
  • the main product is alcohol, especially at high conversions and/or in the vapour phase.
  • conversions and selectivities have been calculated as, respectively, the proportion of carboxylic acid hydrogenated, and the proportion of the hydrogenated carboxylic which is not converted into alkane by product.
  • selectivity denotes the ability of the catalyst to carry out hydrogenation without alkanation. In all examples (unless stated otherwise) only trace amounts ( ⁇ 2%) of dialkyl ether and aldehyde are formed.
  • the catalysts of procedures A and B of Example 1 were tested for activity in the hydrogenation of acetic acid at 10.3 barg.
  • Catalysts prepared by procedures D and E of Example 1 were each employed for the hydrogenation of heptanoic acid in the liquid phase. Reactions were carried out in high pressure autoclaves of approximately 80 mls capacity. In each case 20 g n-heptanoic acid and 0.5 g catalyst were charged to the reactor, the vessel was flushed and pressurised with hydrogen gas, and then heated at 230°C for 12 hours. The vessel was then cooled, and the products recovered and analysed by glc. The product was found to contain n-heptylheptanoate. Evidently, n-heptanol product undergoes esterification in situ with unreacted acid.
  • Example 1 was studied for the vapour phase hydrogenation of acetic acid.
  • the experimental details were as for Examples 2-8. Results are reported in Table 3.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Claims (17)

1. Verfahren zur Herstellung eines Alkohols und/oder eines Carbonsäureesters aus einer C₂ bis C12 Carbonsäure durch In-Berührung-Bringen der Carbonsäure bei erhöhter Temperatur und erhöhtem Druck mit Wasserstoff in Gegenwart eines heterogenen Katalysators, dadurch gekennzeichnet, daß der Katalysator eine erste Komponente, die entweder Molybdän oder Wolfram ist, und eine zweite Komponente, die ein Edelmetall aus der Gruppe VIII des Periodensystems der Elemente ist, umfaßt.
2. Verfahren nach Anspruch 1, worin die zweite Komponente entweder Palladium, Rhodium oder Ruthenium ist.
3. Verfahren nach Anspruch 1 oder 2, worin der Katalysator eine dritte Komponente umfaßt, die ein Träger ist.
4. Verfahren nach Anspruch 3, worin der Träger graphitierter Kohlenstoff mit hoher Oberfläche ist.
5. Verfahren nach Anspruch 3, worin der Träger ein Siliziumdioxid ist.
6. Verfahren nach einem der vorstehenden Ansprüche, worin der Katalysator durch Aufnahme eines oder mehrerer der Metalle aus den Gruppen IA, IIA oder IVA des Periodensystems modifiziert ist.
7. Verfahren nach Anspruch 6, worin das modifizierende Metall Kalium ist.
8. Verfahren zur Herstellung eines Katalysators zur Anwendung im Verfahren nach Anspruch 1, welches Verfahren die folgenden Stufen umfaßt :
(A) Imprägnieren eines Trägers mit einer Lösung einer löslichen Edelmetallverbindung, die thermisch zum Metall zersetzbar/reduzierbar ist, und anschließendes Abtrennen des Lösungsmittels vom Träger,
(B) Erhitzen des Gruppe VIII-Edelmetalles auf dem Träger, und
(C) Imprägnieren des mit dem Edelmetall imprägnierten Trägers mit einer Lösung einer löslichen Molybdän- oder Wolframverbindung, die thermisch zu dem Metall und/oder Oxid zersetzbar/resuzierbar ist, und anschließendes Entfernen des Lösungsmittels vom Träger.
9. Verfahren nach Anspruch 8, worin das Gruppe VIII-Edelmetall auf dem Träger auf eine erhöhte Temperatur im Bereich von 150 bis 350°C in Gegenwart eines Inertgases erhitzt wird.
10. Verfahren nach Ansprunch 8, worin das Gruppe VIII-Edelmetall auf dem Träger auf eine erhöhte Temperatur im Bereich von 100 bis 350°C in Gegenwart eines reduzierenden Gases erhitzt wird.
11. Verfahren nach Anspruch 8, worin das Gruppe VIII-Edelmetall auf dem Träger auf eine erhöhte Temperatur im Bereich von 100 bis 300°C in Gegenwart eines Sauerstoff-hältigen Gases erhitzt wird, mit der Maßgabe, daß dann, wenn der Träger graphitierter Kohlenstoff mit hoher Oberfläche ist, die obere Temperaturgrenze 200°C beträgt.
12. Verfahren nach einem der vorstehenden Ansprüche, worin der Katalysator vor dem Einsatz im Verfahren nach Anspruch 1 durch Kontakt mit Wasserstoff bei erhöher Temperatur im Bereich von 200 bis 350°C während einer Zeitdauer von 1 bis 20 Stunden aktiviert wird.
13. Verfahren nach einem der Ansprüche 1 bis 11, worin der Katalysator durch Erhitzen auf die Reaktionstemperatur in Gegenwart der Reaktanten aktiviert wird.
14. Verfahren nach einem der Ansprüche 1 bis 6, worin die erhöhte Temperatur im Bereich von 150 bis 250°C liegt.
15. Verfahren nach einem der Ansprüche 1 bis 6 und 10, worin die Carbonsäure in der Dampfphase mit Wasserstoff in Berührung gebracht wird.
16. Verfahren nach Anspruch 1, bei Ausführung in flüssiger Phase bei niedrigen Umwandlungsgraden zur Herstellung eines Produktes, das im wesentlichen einen Carbonsäureester umfaßt.
17. Ein Katalysator zur Anwendung im Verfahren nach Anspruch 1, umfassend eine erste Komponente, die entweder Molybdän oder Wolfram ist, und eine zweite Komponente, die ein Edelmetall aus der Gruppe VIII des Periodensystems der Elemente ist.
EP86302692A 1985-04-13 1986-04-11 Alkoholherstellung durch Hydrogenierung von Carbonsäuren Expired - Lifetime EP0198682B1 (de)

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AT86302692T ATE61327T1 (de) 1985-04-13 1986-04-11 Alkoholherstellung durch hydrogenierung von carbonsaeuren.

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GB8509530 1985-04-13
GB858509530A GB8509530D0 (en) 1985-04-13 1985-04-13 Hydrogenation of carboxylic acids

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EP0198682A3 EP0198682A3 (en) 1988-06-08
EP0198682B1 true EP0198682B1 (de) 1991-03-06

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JP (2) JPS61275234A (de)
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AT (2) ATE94861T1 (de)
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US8614359B2 (en) 2011-11-09 2013-12-24 Celanese International Corporation Integrated acid and alcohol production process
US8637714B2 (en) 2008-07-31 2014-01-28 Celanese International Corporation Process for producing ethanol over catalysts containing platinum and palladium
US8658843B2 (en) 2011-10-06 2014-02-25 Celanese International Corporation Hydrogenation catalysts prepared from polyoxometalate precursors and process for using same to produce ethanol while minimizing diethyl ether formation
US8664454B2 (en) 2010-07-09 2014-03-04 Celanese International Corporation Process for production of ethanol using a mixed feed using copper containing catalyst
US8668750B2 (en) 2010-02-02 2014-03-11 Celanese International Corporation Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels
US8680343B2 (en) 2010-02-02 2014-03-25 Celanese International Corporation Process for purifying ethanol
US8680321B2 (en) 2009-10-26 2014-03-25 Celanese International Corporation Processes for making ethanol from acetic acid using bimetallic catalysts
US8680317B2 (en) 2008-07-31 2014-03-25 Celanese International Corporation Processes for making ethyl acetate from acetic acid
US8680342B2 (en) 2010-05-07 2014-03-25 Celanese International Corporation Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water
US8686199B2 (en) 2011-04-26 2014-04-01 Celanese International Corporation Process for reducing the concentration of acetic acid in a crude alcohol product
US8686200B2 (en) 2011-04-26 2014-04-01 Celanese International Corporation Process to recover alcohol from an acidic residue stream
US8686201B2 (en) 2011-11-09 2014-04-01 Celanese International Corporation Integrated acid and alcohol production process having flashing to recover acid production catalyst
US8703868B2 (en) 2011-11-28 2014-04-22 Celanese International Corporation Integrated process for producing polyvinyl alcohol or a copolymer thereof and ethanol
US8704013B2 (en) 2011-11-09 2014-04-22 Celanese International Corporation Integrated process for producing ethanol
US8704008B2 (en) 2010-07-09 2014-04-22 Celanese International Corporation Process for producing ethanol using a stacked bed reactor
US8710279B2 (en) 2010-07-09 2014-04-29 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
US8710277B2 (en) 2009-10-26 2014-04-29 Celanese International Corporation Process for making diethyl ether from acetic acid
US8728179B2 (en) 2010-02-02 2014-05-20 Celanese International Corporation Ethanol compositions
US8747492B2 (en) 2010-02-02 2014-06-10 Celanese International Corporation Ethanol/fuel blends for use as motor fuels
US8754268B2 (en) 2011-04-26 2014-06-17 Celanese International Corporation Process for removing water from alcohol mixtures
US8754267B2 (en) 2010-05-07 2014-06-17 Celanese International Corporation Process for separating acetaldehyde from ethanol-containing mixtures
US8802902B2 (en) 2011-12-30 2014-08-12 Celanese International Corporation Pressure driven distillation for ethanol production and recovery from hydrogenation process
US8809598B2 (en) 2011-11-09 2014-08-19 Celanese International Corporation Producing ethanol using two different streams from acetic acid carbonylation process
US8809599B2 (en) 2011-11-09 2014-08-19 Celanese International Corporation Integrated process for producing ethanol and water balance control
US8846988B2 (en) 2010-07-09 2014-09-30 Celanese International Corporation Liquid esterification for the production of alcohols
US8858659B2 (en) 2010-02-02 2014-10-14 Celanese International Corporation Processes for producing denatured ethanol
US8884081B2 (en) 2011-04-26 2014-11-11 Celanese International Corporation Integrated process for producing acetic acid and alcohol
US8895786B2 (en) 2011-08-03 2014-11-25 Celanese International Corporation Processes for increasing alcohol production
US8907141B2 (en) 2011-04-26 2014-12-09 Celanese International Corporation Process to recover alcohol with secondary reactors for esterification of acid
US8907142B2 (en) 2011-12-29 2014-12-09 Celanese International Corporation Process for promoting catalyst activity for ethyl acetate conversion
US8927787B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process for controlling a reboiler during alcohol recovery and reduced ester formation
US8927784B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process to recover alcohol from an ethyl acetate residue stream
US8927788B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process to recover alcohol with reduced water from overhead of acid column
US8932372B2 (en) 2010-02-02 2015-01-13 Celanese International Corporation Integrated process for producing alcohols from a mixed acid feed
US8933278B2 (en) 2011-04-26 2015-01-13 Celanese International Corporation Process for producing ethanol and reducing acetic acid concentration
US9000232B2 (en) 2011-04-26 2015-04-07 Celanese International Corporation Extractive distillation of crude alcohol product
US9000233B2 (en) 2011-04-26 2015-04-07 Celanese International Corporation Process to recover alcohol with secondary reactors for hydrolysis of acetal
US9000234B2 (en) 2011-12-22 2015-04-07 Celanese International Corporation Calcination of modified support to prepare hydrogenation catalysts
US9024083B2 (en) 2010-07-09 2015-05-05 Celanese International Corporation Process for the production of ethanol from an acetic acid feed and a recycled ethyl acetate feed
US9024082B2 (en) 2011-04-26 2015-05-05 Celanese International Corporation Using a dilute acid stream as an extractive agent
US9024084B2 (en) 2011-04-26 2015-05-05 Celanese International Corporation Reduced energy alcohol separation process having controlled pressure
US9024085B2 (en) 2011-04-26 2015-05-05 Celanese International Corporation Process to reduce ethanol recycled to hydrogenation reactor
US9050585B2 (en) 2012-02-10 2015-06-09 Celanese International Corporation Chemisorption of ethyl acetate during hydrogenation of acetic acid to ethanol
US9051235B2 (en) 2012-02-07 2015-06-09 Celanese International Corporation Process for producing ethanol using a molar excess of hydrogen
US9073816B2 (en) 2011-04-26 2015-07-07 Celanese International Corporation Reducing ethyl acetate concentration in recycle streams for ethanol production processes
US9233899B2 (en) 2011-12-22 2016-01-12 Celanese International Corporation Hydrogenation catalysts having an amorphous support
US9272970B2 (en) 2010-07-09 2016-03-01 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes

Families Citing this family (191)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8509530D0 (en) * 1985-04-13 1985-05-15 Bp Chem Int Ltd Hydrogenation of carboxylic acids
JPS63179845A (ja) * 1986-08-14 1988-07-23 Idemitsu Kosan Co Ltd カルボン酸エステルの製造方法
GB8707595D0 (en) * 1987-03-31 1987-05-07 British Petroleum Co Plc Chemical process
US5149680A (en) * 1987-03-31 1992-09-22 The British Petroleum Company P.L.C. Platinum group metal alloy catalysts for hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters
GB8811009D0 (en) * 1988-05-10 1988-06-15 Bp Chem Int Ltd Chemical process
US5114902A (en) * 1990-01-29 1992-05-19 Syracuse University Process of making supported catalyst
DE4039026A1 (de) * 1990-12-07 1992-06-11 Bayer Ag Verfahren zur herstellung von anilin
US5234584A (en) * 1991-02-04 1993-08-10 United Technologies Corporation Catalytic oxidation of aqueous organic contaminants
US5298343A (en) * 1992-06-19 1994-03-29 Ecole Polytechnique De Montreal Electrocatalysts for H2 /O2 fuel cells cathode
JP3381804B2 (ja) * 1993-07-27 2003-03-04 荒川化学工業株式会社 カルボン酸直接還元用触媒および該触媒の製造方法ならびにアルコール化合物の製造方法
WO1995024371A1 (fr) * 1994-03-09 1995-09-14 Sagami Chemical Research Center Procede de production d'alcool
US5405992A (en) * 1994-04-28 1995-04-11 Uop Process for concurrent esterification and separation using a simulated moving bed
US5510524A (en) * 1995-02-21 1996-04-23 Bp Chemicals Limited Process for the production of a carboxylic acid
SE9602484D0 (sv) * 1996-06-24 1996-06-24 Eka Chemicals Ab Method of producing a chemical compound
US6486367B1 (en) 1997-12-01 2002-11-26 The Standard Oil Company Process for the hydrogenation of maleic acid to 1,4-butanediol
DE19803892A1 (de) * 1998-01-31 1999-08-05 Bayer Ag Verfahren zur Herstellung von optisch aktiven Aminoalkoholen
US6168775B1 (en) * 1998-08-26 2001-01-02 Hydrocarbon Technologies, Inc. Catalyst and process for direct catalystic production of hydrogen peroxide, (H2O2)
US6576214B2 (en) * 2000-12-08 2003-06-10 Hydrocarbon Technologies, Inc. Catalytic direct production of hydrogen peroxide from hydrogen and oxygen feeds
US6455742B1 (en) 1999-09-02 2002-09-24 Wisconsin Alumni Research Foundation Method for catalytically reducing carboxylic acid groups to hydroxyl groups in hydroxycarboxylic acids
DE10014646A1 (de) * 2000-03-24 2001-09-27 Basf Ag Verfahren zur Herstellung von Alkoholen an rheniumhaltigen Aktivkohle-Trägerkatalysatoren
ITMI20012565A1 (it) * 2001-12-05 2003-06-05 Univ Degli Studi Milano Catalizzatori per la sintesi dell'ammoniaca
US6746597B2 (en) * 2002-01-31 2004-06-08 Hydrocarbon Technologies, Inc. Supported noble metal nanometer catalyst particles containing controlled (111) crystal face exposure
MXPA05004561A (es) * 2002-11-01 2005-07-26 Cargill Inc Proceso para preparacion de 1,3-propanoidal.
US7345005B2 (en) * 2003-02-13 2008-03-18 E.I. Du Pont De Nemours And Company Electrocatalysts and processes for producing
US7067103B2 (en) 2003-03-28 2006-06-27 Headwaters Nanokinetix, Inc. Direct hydrogen peroxide production using staged hydrogen addition
US20040220052A1 (en) * 2003-04-29 2004-11-04 Bright Instruments Corp. Water gas shift reaction catalysts
US7655137B2 (en) 2003-07-14 2010-02-02 Headwaters Technology Innovation, Llc Reforming catalysts having a controlled coordination structure and methods for preparing such compositions
US7045479B2 (en) * 2003-07-14 2006-05-16 Headwaters Nanokinetix, Inc. Intermediate precursor compositions used to make supported catalysts having a controlled coordination structure and methods for preparing such compositions
US7011807B2 (en) * 2003-07-14 2006-03-14 Headwaters Nanokinetix, Inc. Supported catalysts having a controlled coordination structure and methods for preparing such catalysts
US7569508B2 (en) * 2004-11-17 2009-08-04 Headwaters Technology Innovation, Llc Reforming nanocatalysts and method of making and using such catalysts
US7144565B2 (en) * 2003-07-29 2006-12-05 Headwaters Nanokinetix, Inc. Process for direct catalytic hydrogen peroxide production
US7045670B2 (en) * 2003-09-03 2006-05-16 Synfuels International, Inc. Process for liquid phase hydrogenation
US7632775B2 (en) * 2004-11-17 2009-12-15 Headwaters Technology Innovation, Llc Multicomponent nanoparticles formed using a dispersing agent
US7718309B2 (en) * 2004-12-06 2010-05-18 Honda Motor Co., Ltd. Platinum and tungsten containing electrocatalysts
US7736790B2 (en) * 2004-12-06 2010-06-15 Honda Motor Co., Ltd. Platinum and tungsten containing electrocatalysts
US7449423B2 (en) * 2005-01-14 2008-11-11 Headwaters Technology Innovation, Llc Heat treatment of anchored nanocatalysts in a non-zero oxidation state and catalysts made by such method
CA2598306C (en) * 2005-02-21 2013-06-04 Nissan Motor Co., Ltd. Electrode catalyst and method for producing same
US7045481B1 (en) 2005-04-12 2006-05-16 Headwaters Nanokinetix, Inc. Nanocatalyst anchored onto acid functionalized solid support and methods of making and using same
US7435504B2 (en) * 2005-08-25 2008-10-14 Honda Motor Co., Ltd. Platinum, tungsten, and nickel or zirconium containing electrocatalysts
US7396795B2 (en) * 2005-08-31 2008-07-08 Headwaters Technology Innovation, Llc Low temperature preparation of supported nanoparticle catalysts having increased dispersion
US7288500B2 (en) * 2005-08-31 2007-10-30 Headwaters Technology Innovation, Llc Selective hydrogenation of nitro groups of halonitro aromatic compounds
US7935652B2 (en) * 2005-09-15 2011-05-03 Headwaters Technology Innovation, Llc. Supported nanoparticle catalysts manufactured using caged catalyst atoms
US7892299B2 (en) * 2005-09-15 2011-02-22 Headwaters Technology Innovation, Llc Methods of manufacturing fuel cell electrodes incorporating highly dispersed nanoparticle catalysts
US7718710B2 (en) * 2006-03-17 2010-05-18 Headwaters Technology Innovation, Llc Stable concentrated metal colloids and methods of making same
US7632774B2 (en) * 2006-03-30 2009-12-15 Headwaters Technology Innovation, Llc Method for manufacturing supported nanocatalysts having an acid-functionalized support
US7541309B2 (en) * 2006-05-16 2009-06-02 Headwaters Technology Innovation, Llc Reforming nanocatalysts and methods of making and using such catalysts
DE102006026947B4 (de) * 2006-06-09 2014-01-23 Karlsruher Institut für Technologie Verwendung eines multifunktionellen Katalysators
US7563742B2 (en) 2006-09-22 2009-07-21 Headwaters Technology Innovation, Llc Supported nickel catalysts having high nickel loading and high metal dispersion and methods of making same
US7601668B2 (en) 2006-09-29 2009-10-13 Headwaters Technology Innovation, Llc Methods for manufacturing bi-metallic catalysts having a controlled crystal face exposure
WO2008097586A2 (en) * 2007-02-06 2008-08-14 The Ohio State University Research Foundation Endolumenal restriction method and apparatus
US7425657B1 (en) * 2007-06-06 2008-09-16 Battelle Memorial Institute Palladium catalyzed hydrogenation of bio-oils and organic compounds
US7615671B2 (en) 2007-11-30 2009-11-10 Eastman Chemical Company Hydrogenation process for the preparation of 1,2-diols
US7816565B2 (en) 2008-07-31 2010-10-19 Celanese International Corporation Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst
US7863489B2 (en) * 2008-07-31 2011-01-04 Celanese International Corporation Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
US7608744B1 (en) 2008-07-31 2009-10-27 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US7820852B2 (en) * 2008-07-31 2010-10-26 Celanese International Corporation Direct and selective production of ethyl acetate from acetic acid utilizing a bimetal supported catalyst
US20100197486A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
US7855303B2 (en) * 2008-11-14 2010-12-21 Celanese International Corporation Integrated process for the production of vinyl acetate from acetic acid via ethylene
KR101140545B1 (ko) * 2008-12-12 2012-05-02 에스케이이노베이션 주식회사 카르복시산으로부터 단일 공정을 통해 알코올을 제조하는 방법
US8178715B2 (en) * 2008-12-31 2012-05-15 Celanese International Corporation Integrated process for the production of vinyl acetate from acetic acid via acetaldehyde
US7820853B2 (en) * 2008-12-31 2010-10-26 Celanese International Corporation Integrated process for the production of vinyl acetate from acetic acid via ethyl acetate
JP2010239913A (ja) * 2009-04-08 2010-10-28 Shiro Saka 有機酸発酵および直接水素化分解によるアルコール類の製造方法
CN102307657B (zh) * 2009-10-26 2014-10-08 国际人造丝公司 使用酸性催化剂由乙酸制备乙醇的方法
WO2011053365A1 (en) 2009-10-26 2011-05-05 Celanese International Corporation Processes for making ethanol from acetic acid
EP2493606A2 (de) * 2009-10-26 2012-09-05 Celanese International Corporation Katalysatoren zur herstellung von ethanol aus essigsäure
BR112012009770A2 (pt) * 2009-10-26 2016-05-17 Celanese Int Corp catalisador para a produçao de etanol através da hidrogenação de ácio acético que compreende platina-estanho sobre suporte de silício
CA2778771A1 (en) * 2009-10-26 2011-05-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
EP2493611A2 (de) 2009-10-26 2012-09-05 Celanese International Corporation Verfahren zur herstellung von ethanol oder ethylacetat aus essigsäure mithilfe bimetallischer katalysatoren
EP2493607A1 (de) * 2009-10-26 2012-09-05 Celanese International Corporation Verfahren zur herstellung von ethylacetat aus essigsäure
TWI419871B (zh) * 2009-12-01 2013-12-21 Celanese Int Corp 由醋酸經乙烯而產製醋酸乙烯酯之整合性製程
US8318988B2 (en) 2010-05-07 2012-11-27 Celanese International Corporation Process for purifying a crude ethanol product
US8552226B2 (en) 2010-02-02 2013-10-08 Celanese International Corporation Process for heat integration for ethanol production and purification process
US8394985B2 (en) * 2010-02-02 2013-03-12 Celanese International Corporation Process for producing an ester feed stream for esters production and co-production of ethanol
SG182738A1 (en) * 2010-02-02 2012-08-30 Celanese Int Corp Process for purifying a crude ethanol product
US8552224B2 (en) 2010-05-07 2013-10-08 Celanese International Corporation Processes for maximizing ethanol formation in the hydrogenation of acetic acid
US8552225B2 (en) 2010-02-02 2013-10-08 Celanese International Corporation Process for vaporizing acetic acid for hydrogenation processes to produce ethanol
JP2013518819A (ja) * 2010-02-02 2013-05-23 セラニーズ・インターナショナル・コーポレーション 変性エタノールの製造方法
US8394984B2 (en) * 2010-02-02 2013-03-12 Celanese International Corporation Process for producing an ethyl acetate solvent and co-production of ethanol
BR112012026991B1 (pt) 2010-04-21 2021-08-31 Sk Innovation Co., Ltd Método para preparação de catalisador a base de cobre, catalisador a base de cobre, uso de catalisador a base de cobre e método para preparação de álcool
US8575404B2 (en) 2010-05-07 2013-11-05 Celanese International Corporation Process for recycling gas from acetic acid hydrogenation
US8704010B2 (en) * 2010-05-07 2014-04-22 Celanese International Corporation Alcohol production process with impurity removal
US8704011B2 (en) 2010-05-07 2014-04-22 Celanese International Corporation Separating ethanol and ethyl acetate under low pressure conditions
US8604255B2 (en) 2010-05-07 2013-12-10 Celanese International Corporation Process for recovering ethanol with sidedraws to regulate C3+ alcohols concentrations
US9150474B2 (en) 2010-07-09 2015-10-06 Celanese International Corporation Reduction of acid within column through esterification during the production of alcohols
US8809597B2 (en) 2010-07-09 2014-08-19 Celanese International Corporation Separation of vapor crude alcohol product
CA2800319A1 (en) 2010-07-09 2012-01-12 Celanese International Corporation Finishing reactor for purifying ethanol
US8884080B2 (en) 2010-07-09 2014-11-11 Celanese International Corporation Reduced energy alcohol separation process
US8536384B2 (en) 2010-07-09 2013-09-17 Celanese International Corporation Recovering ethanol sidedraw by separating crude product from hydrogenation process
US9126125B2 (en) 2010-07-09 2015-09-08 Celanese International Corporation Reduced energy alcohol separation process having water removal
US8846986B2 (en) 2011-04-26 2014-09-30 Celanese International Corporation Water separation from crude alcohol product
US8859827B2 (en) 2011-11-18 2014-10-14 Celanese International Corporation Esterifying acetic acid to produce ester feed for hydrogenolysis
US8901358B2 (en) 2010-07-09 2014-12-02 Celanese International Corporation Esterification of vapor crude product in the production of alcohols
US8710280B2 (en) 2010-07-09 2014-04-29 Celanese International Corporation Weak acid recovery system for ethanol separation processes
JP2012050924A (ja) * 2010-08-31 2012-03-15 National Institute Of Advanced Industrial Science & Technology 超臨界水を反応場とするリグニンのガス化触媒及びリグニンのガス化方法
CN102688758A (zh) * 2011-03-22 2012-09-26 中国科学院大连化学物理研究所 一种乙酸气相加氢制取乙醇的催化剂及其制备方法
CN102690170B (zh) * 2011-03-22 2015-03-04 中国科学院大连化学物理研究所 一种由乙酸气相加氢制备乙醇的方法
CN102228831A (zh) * 2011-04-25 2011-11-02 中国科学院大连化学物理研究所 一种乙酸气相加氢制取乙醇的催化剂
CN102229520B (zh) * 2011-04-25 2013-12-11 江苏索普（集团）有限公司 一种由醋酸气相加氢制备乙醇的方法
US8927780B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process for removing aldehydes from ethanol reaction mixture
US8461399B2 (en) 2011-04-26 2013-06-11 Celanese International Corporation Separation process having an alcohol sidestream
US8748675B2 (en) 2011-06-16 2014-06-10 Celanese International Corporation Extractive distillation of crude alcohol product
US8927783B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Recovering ethanol with sidestreams to regulate C3+ alcohols concentrations
US8704012B2 (en) 2011-06-16 2014-04-22 Celanese International Corporation Distillation of crude alcohol product using entrainer
US8748676B2 (en) 2011-08-03 2014-06-10 Celanese International Corporation Process for purifying a crude ethanol product
US8884079B2 (en) 2011-08-03 2014-11-11 Celanese International Corporation Reducing impurities in hydrogenation processes with multiple reaction zones
US8927782B2 (en) 2011-08-03 2015-01-06 Celanese International Corporation Vapor separation in alcohol production
US8877986B2 (en) 2011-08-03 2014-11-04 Celanese International Corporation Process for recovering alcohol
US8877987B2 (en) 2011-08-03 2014-11-04 Celanese International Corportation Process for producing anhydrous ethanol using extractive distillation column
US8440866B2 (en) 2011-08-03 2013-05-14 Celanese International Corporation Process for separating ethanol having low acid
US8575405B2 (en) 2011-08-03 2013-11-05 Celanese International Corporation Reducing acetals during ethanol separation process
US8853467B2 (en) 2011-08-19 2014-10-07 Celanese International Corporation Integrated process for producing ethanol
US8853466B2 (en) 2011-08-19 2014-10-07 Celanese International Corporation Integrated process for producing ethanol from methanol
US8829253B2 (en) 2011-08-19 2014-09-09 Celanese International Corporation Integrated process for producing ethanol from methanol
US9109174B2 (en) 2011-09-20 2015-08-18 Phillips 66 Company Advanced cellulosic renewable fuels
WO2013056268A2 (en) 2011-10-06 2013-04-18 Celanese International Corporation Hydrogenation catalysts prepared from polyoxometalate precursors and process for using same to produce ethanol
US8748673B2 (en) 2011-11-18 2014-06-10 Celanese International Corporation Process of recovery of ethanol from hydrogenolysis process
US8853468B2 (en) 2011-11-18 2014-10-07 Celanese International Corporation Vapor esterification method to produce ester feed for hydrogenolysis
US8829249B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Integrated esterification and hydrogenolysis process for producing ethanol
US8829251B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Liquid esterification method to produce ester feed for hydrogenolysis
US8802901B2 (en) 2011-11-18 2014-08-12 Celanese International Corporation Continuous ethyl acetate production and hydrogenolysis thereof
US9024089B2 (en) 2011-11-18 2015-05-05 Celanese International Corporation Esterification process using extractive separation to produce feed for hydrogenolysis
US20130131399A1 (en) 2011-11-23 2013-05-23 Celanese International Corporation Catalyst Preparations for High Conversion Catalysts for Producing Ethanol
US8927790B2 (en) 2011-12-15 2015-01-06 Celanese International Corporation Multiple vapor feeds for hydrogenation process to produce alcohol
US8637715B2 (en) 2011-12-21 2014-01-28 Celanese International Corporation Catalysts comprising secondary noble metals and process for producing ethanol
US8575406B2 (en) 2011-12-22 2013-11-05 Celanese International Corporation Catalysts having promoter metals and process for producing ethanol
WO2013095963A1 (en) 2011-12-22 2013-06-27 Celanese International Corporation Ethanol process using hydrogenation catalysts having an amorphous support
US9079172B2 (en) 2012-03-13 2015-07-14 Celanese International Corporation Promoters for cobalt-tin catalysts for reducing alkanoic acids
US9333496B2 (en) 2012-02-29 2016-05-10 Celanese International Corporation Cobalt/tin catalyst for producing ethanol
US8455702B1 (en) 2011-12-29 2013-06-04 Celanese International Corporation Cobalt and tin catalysts for producing ethanol
WO2013103395A1 (en) * 2012-01-06 2013-07-11 Celanese International Corporation Precious metal, active metal and modified support - containing hydrogenation catalysts and acetic acid hydrogenation process using the same
SG11201403768UA (en) 2012-01-06 2014-10-30 Celanese Int Corp Cobalt-containing hydrogenation catalysts and processes for making same
WO2013103394A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Processes for making catalysts with metal halide precursors
US20130178667A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Processes for Making Catalysts
WO2013103398A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Modified catalyst supports and process for producing ethanol using the catalyst
US8981164B2 (en) 2012-01-06 2015-03-17 Celanese International Corporation Cobalt and tin hydrogenation catalysts
CN103874545B (zh) * 2012-01-06 2016-08-24 国际人造丝公司 利用由多金属氧酸盐前体制备的加氢催化剂生产乙醇的方法
BR112014016770A2 (pt) * 2012-01-06 2017-06-13 Celanese International Corporation catalisador de hidrogenação
US8937203B2 (en) 2012-01-06 2015-01-20 Celanese International Corporation Multifunctional hydrogenation catalysts
WO2013103396A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Processes for making catalysts with oxalate precursors
US9024086B2 (en) 2012-01-06 2015-05-05 Celanese International Corporation Hydrogenation catalysts with acidic sites
US8802588B2 (en) 2012-01-23 2014-08-12 Celanese International Corporation Bismuth catalyst composition and process for manufacturing ethanol mixture
US20130197278A1 (en) 2012-01-27 2013-08-01 Celanese International Corporation Process For Manufacturing Ethanol Using A Metallic Catalyst Supported on Titania
US9353034B2 (en) 2012-02-07 2016-05-31 Celanese International Corporation Hydrogenation process with reduced residence time for vapor phase reactants
US8729311B2 (en) 2012-02-10 2014-05-20 Celanese International Corporaton Catalysts for converting acetic acid to acetone
US8729317B2 (en) 2012-02-15 2014-05-20 Celanese International Corporation Ethanol manufacturing process over catalyst with cesium and support comprising tungsten or oxides thereof
CN103288596B (zh) * 2012-02-27 2015-08-26 中国科学院大连化学物理研究所 一种有机酸加氢制备一元醇或二元醇的方法
US9126194B2 (en) 2012-02-29 2015-09-08 Celanese International Corporation Catalyst having support containing tin and process for manufacturing ethanol
US20130225876A1 (en) 2012-02-29 2013-08-29 Celanese International Corporation Hydrogenation Catalyst Using Multiple Impregnations of an Active Metal Solution
US8927786B2 (en) 2012-03-13 2015-01-06 Celanese International Corporation Ethanol manufacturing process over catalyst having improved radial crush strength
US8802903B2 (en) 2012-03-13 2014-08-12 Celanese International Corporation Stacked bed reactor with diluents for producing ethanol
US8536383B1 (en) 2012-03-14 2013-09-17 Celanese International Corporation Rhodium/tin catalysts and processes for producing ethanol
US9073042B2 (en) 2012-03-14 2015-07-07 Celanese International Corporation Acetic acid hydrogenation over a group VIII metal calcined catalyst having a secondary promoter
US20130261349A1 (en) 2012-03-28 2013-10-03 Celanese International Corporation Hydrogenation Catalysts and Processes for Making Same
US8975452B2 (en) 2012-03-28 2015-03-10 Celanese International Corporation Process for producing ethanol by hydrocarbon oxidation and hydrogenation or hydration
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU420326A1 (ru) * 1972-12-28 1974-03-25 Д. В. Сокольский, В. К. Орлов, К. А. Жубанов, Ф. Г. Голодов, СПОСОБ ПРИГОТОВЛЕНИЯ КАТАЛИЗАТОРА ДЛЯ ГИДРИРОВАНИЯ ОРГАНИЧЕСКИХ СОЕДИНЕНИЙО^П"''ч- у;: • ^

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2322095A (en) * 1925-11-20 1943-06-15 Gen Aniline & Film Corp Catalytic hydrogenation of organic compounds
US1839974A (en) * 1931-03-05 1932-01-05 Du Pont Hydrogenation of carboxylic acids
GB433549A (en) * 1934-02-16 1935-08-16 Ici Ltd Process for reducing fatty acids and esters thereof
GB457358A (en) * 1934-10-11 1936-11-26 Rohm & Haas Improvements in catalytic hydrogenation process
US2861959A (en) * 1952-05-03 1958-11-25 Exxon Research Engineering Co Promoted hydroforming catalyst
BE622853A (de) * 1961-09-02 1900-01-01
US3363009A (en) * 1964-06-08 1968-01-09 Hydrocarbon Research Inc Continuous process for producing detergent grade alcohols and glycerine
US3536632A (en) * 1967-10-10 1970-10-27 Exxon Research Engineering Co Heterogeneous catalysts
CA949544A (en) * 1970-02-13 1974-06-18 Henry Erickson Rhenium and platinum series metal-containing catalysts
US3829448A (en) * 1970-06-18 1974-08-13 Mitsubishi Petrochemical Co Process for producing ypsilon-lactones and cyclic ethers
CA965766A (en) * 1970-06-22 1975-04-08 Akio Furuta Ammonia synthesis catalyst and process
US3661769A (en) * 1970-11-23 1972-05-09 Mobil Oil Corp Process for reforming a naphtha feedstock in the presence of a platinumtungsten-alumina catalyst
JPS5543262B2 (de) * 1972-08-23 1980-11-05
JPS49102606A (de) * 1973-02-15 1974-09-27
US4039572A (en) * 1974-03-19 1977-08-02 Teijin Limited Process for preparing diesters of carboxylic acids by catalytic oxidative carbonylation
DE2519817A1 (de) * 1975-05-03 1976-11-11 Hoechst Ag Verfahren zur herstellung von butandiol-(1.4)
DE2605107C3 (de) * 1976-02-10 1983-12-29 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Herstellung von Diolen durch katalytische Hydrierung der entsprechenden Dicarbonsäuren
GB1565074A (en) * 1976-11-03 1980-04-16 British Petroleum Co Process for the production of ammonia
US4165276A (en) * 1977-09-14 1979-08-21 Uop Inc. Hydrocarbon conversion with a superactive multimetallic catalytic composite
US4176488A (en) * 1977-10-28 1979-12-04 Fuji Kogyo Co., Ltd. Line guide ring
US4104478A (en) * 1977-11-23 1978-08-01 Ashland Oil, Inc. Catalytic hydrogenation of fatty acids
US4176088A (en) * 1978-03-20 1979-11-27 Uop Inc. Superactive multimetallic catalytic composite comprising platinum group metal and rhenium
US4359404A (en) * 1980-03-24 1982-11-16 Allied Corporation Hydrogenation of esters using alkali doped heterogeneous Group VIII transition metal catalysts
US4500650A (en) * 1981-01-20 1985-02-19 Johnson Matthey Public Limited Company Three-way catalysts for purification of exhaust gas and method for the preparation of the catalysts
US4338221A (en) * 1981-02-11 1982-07-06 Uop Inc. Catalyst for the reduction of unsaturated organic acids
US4340546A (en) * 1981-03-09 1982-07-20 Uop Inc. Process for the reduction of unsaturated carboxylic acids
JPS57180435A (en) * 1981-04-30 1982-11-06 Sumitomo Chem Co Ltd Rhenium type catalytic composition
FR2505819A1 (fr) * 1981-05-12 1982-11-19 Inst Francais Du Petrole Procede de fabrication d'alcools par hydrogenation catalytique d'esters d'acides organiques
US4443639A (en) * 1981-05-18 1984-04-17 The Standard Oil Company (Indiana) Hydrogenation of carboxylic acids
US4398039A (en) * 1981-05-18 1983-08-09 The Standard Oil Company Hydrogenation of carboxylic acids
FR2527200A1 (fr) * 1982-05-24 1983-11-25 Inst Francais Du Petrole Procede catalytique de production d'alcools par hydrogenolyse d'esters d'acides carboxyliques
US4550185A (en) * 1983-12-22 1985-10-29 E. I. Du Pont De Nemours And Company Process for making tetrahydrofuran and 1,4-butanediol using Pd/Re hydrogenation catalyst
FR2577217B1 (fr) * 1985-02-08 1987-02-20 Rhone Poulenc Chim Base Procede d'hydrogenation de l'acide acetique
GB8509530D0 (en) * 1985-04-13 1985-05-15 Bp Chem Int Ltd Hydrogenation of carboxylic acids
US4724100A (en) * 1986-03-26 1988-02-09 Sherex Chemical Company, Inc. Liquid phase process for producing esters

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU420326A1 (ru) * 1972-12-28 1974-03-25 Д. В. Сокольский, В. К. Орлов, К. А. Жубанов, Ф. Г. Голодов, СПОСОБ ПРИГОТОВЛЕНИЯ КАТАЛИЗАТОРА ДЛЯ ГИДРИРОВАНИЯ ОРГАНИЧЕСКИХ СОЕДИНЕНИЙО^П"''ч- у;: • ^

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ATE94861T1 (de) 1993-10-15
AU5601386A (en) 1986-10-16
NZ215765A (en) 1988-11-29
EP0198682A2 (de) 1986-10-22
DE3677809D1 (de) 1991-04-11
CN86102420A (zh) 1986-10-08
EP0198681B1 (de) 1993-09-22
GB8509530D0 (en) 1985-05-15
AU592981B2 (en) 1990-02-01
EP0198681A2 (de) 1986-10-22
JPH0825931B2 (ja) 1996-03-13
CN1006788B (zh) 1990-02-14
CN1008088B (zh) 1990-05-23
JPS61275234A (ja) 1986-12-05
CN86102452A (zh) 1986-12-03
NZ215766A (en) 1988-11-29
ATE61327T1 (de) 1991-03-15
CA1264727A (en) 1990-01-23
EP0198681A3 (en) 1988-05-04
EP0198682A3 (en) 1988-06-08
US4990655A (en) 1991-02-05
DE3689050D1 (de) 1993-10-28
US5061671A (en) 1991-10-29
CA1262719A (en) 1989-11-07
US4777303A (en) 1988-10-11
AU592980B2 (en) 1990-02-01
DE3689050T2 (de) 1994-01-13
JPS61275237A (ja) 1986-12-05
US4826795A (en) 1989-05-02
US4804791A (en) 1989-02-14
AU5601286A (en) 1986-10-16

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